JP2672144B2 - Method for producing phloroglucin and resorcin - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing phloroglucin and resorcin, and more particularly to a method capable of producing phloroglucin and resorcin simultaneously and efficiently.

Technical background of the invention Phloroglucin is useful as an intermediate for producing pharmaceuticals, agricultural chemicals and the like.

Such phloroglucin is conventionally 1,3,5-triisopropylbenzene (hereinafter sometimes abbreviated as TIPB).
Is oxidized with molecular oxygen or the like to obtain an oxide containing 1,3,5-tris (1-hydroperoxy-1-methylethyl) benzene (hereinafter sometimes abbreviated as TRHP), It was then produced by acid decomposition (cribage) of this oxide (see, for example, East German Patent No.
See 12,239 and British Patent 751,598).

However, when TIPB is oxidized according to the above method, not only the target trifunctional oxide, trihydroperoxide, but also 1,3-bis (1-hydroperoxy-1-methylethyl) -5- ( 1-hydroxy-1
-Methylethyl) benzene (hereinafter sometimes abbreviated as HDHP) and 1- (1-hydroperoxy-1-methylethyl) -3,5-bis (1-hydroxy-1-methylethyl) benzene (hereinafter, referred to as HDHP). (Sometimes abbreviated as DHHP)
Carbinols corresponding to trifunctional oxides such as [3,5-bis (1-hydroperoxy-1-
Methylethyl) isopropylbenzene] and carbinol corresponding to the bifunctional oxide, and monofunctional oxide [5- (1-hydroperoxy-1-methylethyl) -1,3-diisoproperbenzene] and A large amount of carbinol corresponding to this monofunctional oxide is produced as a by-product.

Therefore, when the oxide obtained by the oxidation of TIPB is directly acid-decomposed according to the above method, a large amount of acid decomposition products other than phloroglucin is contained in the product, and therefore, in this method, high-purity phloroglucin is produced. It was difficult to do.

As a method improved on such a method, a solution containing this oxide is brought into contact with hydrogen peroxide (H ₂ O ₂ ) water containing an acidic catalyst and is again oxidized to obtain a trifunctional oxide. A known method is to selectively generate trihydropyroxide from carbinol and then acid-decompose (cribage) this trihydroxyperoxide (JP-A-58-35135 and JP-A-58-150529). See the bulletin).

However, such a method for producing phloroglucin is:
The freezing point of trihydroperoxide, an oxide of TIPB, is
The temperature is as high as 80 to 90 ° C, and since this compound is difficult to dissolve in a solvent that is stable against the secondary oxidation treatment used by H ₂ O _{2, it} is not possible to add trihydrate to the reaction solution during the secondary oxidation treatment or acid decomposition treatment. Hydroperoxides tend to precipitate, and in such a case the reaction does not proceed smoothly. Further, in order to prevent the precipitation of trihydroxyperoxide, it is possible to use a large amount of solvent, but when a large amount of solvent is used, it is inevitable that a large amount of catalyst must be used during the acid decomposition treatment. In addition, the yield of phloroglucin at the time of acid decomposition is low. Therefore, in order to smoothly carry out the secondary oxidation treatment and the acid decomposition treatment as described above, it is important to find a solvent in which the hydrolyzed peroxide has high solubility and which is stable in the H ₂ O ₂ oxidation treatment.

By the way, m-diisopropylbenzene (hereinafter sometimes simply referred to as "m-DIPB") is a compound having a structure similar to that of TIPB.

Then, m-DIPB is oxidized with molecular oxygen, then again oxidized with hydrogen peroxide, and then acid-decomposed to obtain resorcin.

Then, the present inventor has examined in detail the method for producing phloroglucin from TIPB and the method for producing resorcin from m-DIPB, and as a result, found that the production conditions in both methods are very similar. It was

Furthermore, it was found that the oxide of m-DIPB has a low freezing point of 0 ° C. or lower, and that this oxide is a good solvent for the oxide of TIPB.

OBJECTS OF THE INVENTION An object of the present invention is to provide a method capable of simultaneously and efficiently producing phloroglucin and resorcin.

More specifically, the present invention has a small amount of solvent, particularly a small amount of solvent necessary to maintain the acid decomposition treatment raw material in a uniform solution state, and therefore, the amount of acidic catalyst used in the acid decomposition treatment is small, and the phloroglucin yield is also low. It is an object of the present invention to provide a simultaneous production method of phloroglucin and resorcin which can be increased.

SUMMARY OF THE INVENTION In the present invention, a mixed solution containing an oxide of 1,3,5-triisopropylbenzene and an oxide of m-diisopropylbenzene is brought into contact with a hydrogen peroxide solution containing a first acidic catalyst, H ₂ The method for producing phloroglucin and resorcin at the same time is characterized by comprising an O ₂ oxidation step: and an acid decomposition step of bringing the reaction solution obtained from the above step into contact with a second acidic catalyst.

According to the present invention, phloroglucin and resorcin, which have been conventionally produced individually, can be produced simultaneously and efficiently.

In the production method according to the present invention, dihydroperoxide obtained by oxidizing m-DIPB, that is, 1,3-bis (1-
Hydroperoxy-1-methylethyl) benzene (m-
DHP) or monohydroperoxide, that is, 1- (1-hydroperoxy) -3- (1
-Hydroxy-1-methylethyl) benzene (m-HHP
May be abbreviated as), the freezing point is low, and the above TI
It becomes a good solvent for trihydroperoxides obtained by the oxidation of PB. Therefore, a special solvent is not required to carry out a smooth reaction with H ₂ O ₂ , and the amount of the solvent is reduced, so that it is possible to reduce the amount of the acidic catalyst used for the acid decomposition treatment, In addition, the yield of phloroglucin can be improved.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the method for producing phloroglucin and resorcin according to the present invention will be specifically described.

 The manufacturing method of the present invention will be described with reference to FIG.

In the production method according to the present invention, the raw materials TIPB and m-DI
Primary oxide and m-DI of TIPB obtained by oxidation with PB
Phloroglucin and resorcin are produced by oxidizing a mixed solution containing PB primary oxide with H ₂ O ₂ and then acid-decomposing the secondary oxide in the obtained oxide-containing solution.

The first step according to the present invention is the oxide of TIPB and m-DIPB.
Is a step of catalyzing a mixed solution containing the oxide of Example 1 with hydrogen peroxide solution containing the first acidic catalyst.

TIPB oxide and m-DIPB used in this first step
The mixed solution containing the oxide of TIPB and m-DI was prepared as usual.
It can be prepared by oxidizing PB with alkaline lower molecular oxygen. This process is a so-called primary oxidation process, and is indicated by 1 in FIG.

In the primary oxidation treatment, TIPB and m-DIPB are used. In the present invention, 1 part by weight of m-DI
TIPB is usually 0.1 to 1.5 parts by weight, preferably PB, based on PB.
Used in amounts of 0.3 to 1.2 parts by weight.

The above TIPB and m-DIPB are oxidized using molecular oxygen. Here, air is usually used as molecular oxygen. In the primary oxidation treatment, molecular oxygen is usually used in excess of TIPB and m-DIPB.

Such a primary oxidation treatment is usually performed by heating to a temperature of 60 to 120 ° C, preferably 90 to 110 ° C. At such a temperature, the oxides of TIPB and m-DIPB are in a liquid state. Therefore, this primary oxidation treatment can be performed without using a solvent.

The oxidation reaction time in such primary oxidation treatment is usually 5 to 60 hours, preferably 20 to 45 hours.

By carrying out the oxidation reaction for such a period of time, the target substance, TIPB trihydroperoxide (TRH
P) and m-DIPB dihydroperoxide (m-DHP)
And carbinol (HDHP and DHHP) corresponding to the trifunctional oxides of TIPB which are re-oxidized in the first step according to the present invention and the bifunctional oxide of m-DIPB. The corresponding carbinol (m-HHP) can be produced in high yield.

The above-mentioned primary oxidation treatment can be carried out without using a catalyst or the like. However, if necessary, the reaction can be carried out in the presence of a radical initiator and an aqueous alkali solution.

After the primary oxidation is performed in this manner, a mixture of the oxide of TIPB and the oxide of m-DIPB and an organic solvent are mixed to obtain the oxide of TIPB used in the first step of the present invention. A mixed solution containing an oxide of m-DIPB can be prepared.

The organic solvent used here is preferably a solvent having no reactivity with hydrogen peroxide, and specific examples of such an organic solvent include aromatic solvents such as toluene, xylene and benzene. A solvent may be mentioned. These solvents can be used alone or in combination. Among these solvents, toluene is particularly preferably used.

Such an organic solvent is usually added to 1 part by weight of oxide.
It is used in an amount of 0.3-10.0 parts by weight, preferably 0.5-5.0 parts by weight.

The water produced as a byproduct of the above primary oxidation treatment is
By dissolving the oxide in an organic solvent and allowing it to stand, it is separated into two layers of oil and water, so that it is easily removed.

In the mixed solution containing the oxide of TIPB and the oxide of m-DIPB obtained as described above, usually, TIPB is used in an amount corresponding to the ratio of the amounts of TIPB and m-DIPB used as the raw materials. An oxide and an oxide of m-DIPB are included.

In the present invention, the mixed solution containing the oxide of TIPB and the oxide of m-DIPB is prepared in advance as described above.
It is preferable to prepare by performing primary oxidation by mixing with -DIPB, but it is also possible to separately prepare an oxide of TIPB and an oxide of m-DIPB, and mix and prepare both.

In the first step according to the present invention, the mixed solution containing the oxide of TIPB and the oxide of m-DIPB thus obtained is brought into contact with a hydrogen peroxide solution containing a first acidic catalyst. .

This step is a so-called secondary oxidation treatment and is indicated by 2 in FIG.

In this secondary oxidation treatment, hydrogen peroxide is usually used, but potassium peroxide or the like can also be used in addition to or in addition to this hydrogen peroxide. Among them, it is preferable to use hydrogen peroxide.

For example, since hydrogen peroxide as described above is used as an aqueous solution, a mixed solution containing an oxide of TIPB and an oxide of m-DIPB and an aqueous solution containing hydrogen peroxide can be substantially mixed. None, therefore the reaction separates into two layers.

The first acidic catalyst used in this step is a catalyst for oxidizing carbinol to a hydroperoxide in a mixed solution containing an oxide of TIPB and an oxide of m-DIPB,
Examples of such catalysts include inorganic acids such as sulfuric acid, perchloric acid, hydrochloric acid and phosphoric acid, and organic acids such as chloroacetic acid, paratoluenesulfonic acid and trifluoromethanesulfonic acid. These catalysts can be used alone or in combination, and in the present invention, sulfuric acid, phosphoric acid and perchloric acid are preferably used.

The hydrogen peroxide is usually used in excess with respect to the total number of moles of the carbinols in the oxide of TIPB and the oxide of m-DIPB. Generally, the carbinol corresponding to the trifunctional oxide of TIPB contained in the mixture, and m-DI
It is used in an amount of 1 to 50 equivalents, preferably 1 to 20 equivalents, relative to 1 equivalent of the carbinol group contained in the carbinol corresponding to the bifunctional oxide of PB.

The amount of the first acidic catalyst used varies depending on the reaction conditions, the type of catalyst, etc., but in the aqueous layer solution containing H ₂ O ₂ , the amount is 1 to 20% by weight, preferably 8 to 15% by weight. Used.

The secondary oxidation treatment as described above is usually carried out at a temperature of 20 to 65 ° C, preferably 30 to 60 ° C.

The contact between the mixed solution containing the oxide of TIPB and the oxide of m-DIPB and the hydrogen peroxide solution is performed by stirring the reaction solution separated into the above two layers.

Under the above conditions, the time for the secondary oxidation treatment is
It is usually 1 to 120 minutes, preferably 3 to 20 minutes.

Water is produced during the above-mentioned dioxide treatment. Since this water lowers the hydrogen peroxide concentration in the aqueous solution, it is preferably removed from the reaction system. And such water can be azeotropically removed together with the solvent forming the oil layer, and therefore, the oxide of TIPB and m-DI can be removed.
As the organic solvent used when preparing the mixed solution containing the PB oxide, benzene, toluene, xylene and the like are preferable.

After carrying out such a secondary oxidation treatment, a treatment such as neutralization of the reaction solution is usually conducted to neutralize the acidic catalyst contained in the oil layer. Next, the water layer is removed, and the remaining oil layer is washed with water.

The reaction solution thus obtained contains trihydroperoxide of TIPB, dihydroperoxide of m-DIPB and an organic solvent.

Water and organic solvent contained in such a reaction solution,
It is preferable to remove at least a part thereof. This concentration step is indicated by 3 in FIG.

At this time, the water content in the oxide-containing solution is usually removed to an amount of 3% by weight or less, preferably 1% by weight or less,
The organic solvent is usually removed to an amount of 20 to 90 parts by weight, preferably 30 to 80 parts by weight. By performing dehydration and concentration in this manner, the amount of acidic catalyst required for acid decomposition can be reduced, and the yield of phloroglucin can be increased.

In the second step of the present invention, the reaction solution obtained as described above is contacted with the second acidic catalyst. This step is the so-called cribage reaction, which is designated by 4 in FIG.

Examples of the second acidic catalyst used in this acid decomposition treatment include sulfuric acid, sulfuric acid anhydride, hydrofluoric acid, perchloric acid, boron trifluoride, phosphotungstic acid, p-toluenesulfonic acid, chloroacetic acid, and positive acid. Ion exchange resins, silica-alumina, etc. may be mentioned. Particularly in the present invention, it is preferable to use phosphotungstic acid. Such catalysts can be used alone or in combination.

Such acid decomposition treatment is particularly preferable when the reaction system is uniform because the selectivity to phloroglucin and resorcin is high. Therefore, it is preferable that the acid decomposition treatment is performed in a solvent that dissolves both the oxides and acid decomposition products of TIPB and m-DIPB. It is preferable to use the acidic catalyst of No. 2 by dissolving it. Examples of the solvent added to such a second acidic catalyst include acetone and methyl ethyl ketone, with acetone being particularly preferable.

Such a second acidic catalyst is usually added to the reaction solution in an amount of 0.
It is used in an amount of 001 to 10.0% by weight, preferably 0.01 to 1.0% by weight.

Such acid decomposition reaction is usually 50 to 80 ° C., preferably
It is carried out at a temperature of 55 to 75 ° C.

The acid decomposition reaction is usually completed in 5 to 120 minutes, preferably 10 to 60 minutes.

By such acid decomposition treatment, it is included in the secondary oxide.
Phloroglucin is produced from trihydroperoxide (TRHP) which is an oxide of TIPB, and resorcin is produced in a high yield from dihydroperoxide (m-DHP) which is an oxide of m-DIPB.

After carrying out such an acid decomposition treatment, the acidic catalyst is usually neutralized.

From the reaction solution containing both phloroglucin and resorcin, phloroglucin and resorcin are separated and purified by using a known method such as extraction, crystallization and distillation.

That is, for example, in phloroglucin, after contacting the acid-decomposed product-containing solution with neutralized water, acetone is removed to form a two-layer mixed solution consisting of an oil layer solution and an aqueous layer solution, and this mixed solution is separated if necessary. It is liquefied and then separated and purified by crystallizing the extracted phloroglucin in the aqueous layer solution.

In addition, resorcinol is separated and purified by mixing the oil phase solution obtained in the same manner as described above with the residual solution after crystallization of phloroglucin, removing the solvent from the resulting mixed solution, and further distilling resorcinol. You.

EFFECTS OF THE INVENTION In the production method according to the present invention, only an aromatic solvent, for example, may be used as the solvent for the oxidation reaction of carbinols with H ₂ O ₂ , and the solvent necessary for maintaining the acid decomposition raw material in a uniform solution state. Since the amount is small and therefore the amount of the acidic catalyst can be small and the yield of phloroglucin can be increased, the production cost can be reduced.

Moreover, the production method according to the present invention can efficiently produce phloroglucin and resorcin, which are useful as intermediates for producing pharmaceuticals and agricultural chemicals, simultaneously.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 (1) Primary Oxidation Treatment In a reactor equipped with a stirrer, an air-blown sparger, an alkaline aqueous solution inlet and a reflux condenser, 1,3,5-triisopropylbenzene (purity 95% by weight), 500 g, m -Prepare 500 g of diisopropylbenzene (purity 97% by weight), 400 g of water and 70 g of NaOH aqueous solution (concentration 3.6% by weight), raise the temperature to 100 ° C., and then introduce N ₂ gas into the reactor to obtain 5.5 kg / cm ² Pressurized to G pressure.

After that, maintain this pressure and temperature, 150N air
The reaction was carried out for 36 hours with stirring while blowing at a rate of / hour. During this period, keep the pH of the aqueous layer solution above 9
An OH aqueous solution (concentration 3.6% by weight) was appropriately introduced into the reactor through an alkaline aqueous solution inlet.

The obtained oxidation reaction product (oil layer solution) was 2060 g (water content 37% by weight), and 12% by weight of trihydroperoxide (TRHP) as an oxide of TIPB, 14% by weight of monocarbinol dihydroperoxide (HDHP), It contains 6% by weight of dicarbinol monohydroperoxide (DHHP).
As the oxide of m-DIPB, 22% by weight of dihydroperoxide (m-DHP) and hydroxyperoxide (m-H) were used.
HP) 9% by weight.

The yield of the phloroglucin-based oxidation product based on TIPB calculated by the following formula was 62 mol%.

In addition, the yield of the resorcin-based oxidation product calculated based on m-DIPB was 61 mol% based on the following formula.

(2) H ₂ O ₂ oxidation step The reaction solution (oil layer, obtained by the above-mentioned (1) primary oxidation treatment,
Add 63 parts by weight of toluene to 100 parts by weight of the mixture of the aqueous layer, and add 5 parts.
Stirred at 0 ° C. 126 parts by weight of the oil layer solution obtained by removing the aqueous layer solution which was separated after standing was charged into a reactor equipped with a stirrer and a reflux condenser, and 24% by weight of H ₂ O ₂ and 12% by weight thereof were charged.
Add 210 parts by weight of an aqueous solution containing sulfuric acid of
The reaction was carried out at a temperature of 0 ° C for 15 minutes.

After the reaction was completed, oil-water separation was performed to obtain 127 parts by weight of an oil layer solution and 209 parts by weight of an aqueous layer solution. The TRHP concentration of the oil layer solution was 13.3% by weight, and the m-DHP concentration was 14.4% by weight.

The phloroglucin-based H ₂ O ₂ oxidation yield calculated by the following formula was 80 mol%.

In addition, the resorcin-based H ₂ O ₂ calculated by the following formula
The oxidation yield was 92 mol%.

Neutralize this H ₂ O ₂ oxide (oil layer solution) while maintaining it at a temperature of 50 ° C, then wash with water, distill off some of the water and toluene, and concentrate the oil layer solution, and then carry out the next acid cleavage reaction. Using. At this time, the toluene concentration in the oil layer solution was 40% by weight, and the oil layer solution was liquid at a temperature of 50 ° C.

On the other hand, the aqueous layer solution contained 22% by weight of H ₂ O ₂ and 12% by weight of sulfuric acid, which was dehydrated and concentrated under reduced pressure and added with a concentration of 60% by weight of hydrogen peroxide solution and concentrated sulfuric acid. By doing so, the concentration was adjusted so that it could be used again in the H ₂ O ₂ oxidation reaction.

(3) Cribage reaction step Acetone containing 0.06% by weight of phosphotungstic acid was added to a reactor equipped with a stirrer, a reflux condenser and a raw material supply port.
10 parts by weight of a solution (180 parts by weight) in which 90 parts by weight of the oxidation reaction product obtained in the above (2) H ₂ O ₂ oxidation step and 90 parts by weight of acetone were mixed was added thereto while stirring. Added at a rate of parts by weight / minute.

During this time, the reaction temperature was maintained at a temperature at which acetone in the system was refluxed (initial temperature: 56 ° C., addition completion: 65 ° C.). After the addition is complete
Further, stirring was continued at a temperature of 65 ° C. for 35 minutes to complete the reaction.

The concentration of phloroglucin in the reaction solution at the end of the reaction was
The concentration of resorcin was 1.3% by weight and 2.3% by weight.

The yield of phloroglucin relative to TRHP calculated by the following formula was 63 mol%.

Further, the yield of resorcin based on m-DHP calculated by the following formula was 89 mol%.

(4) Separation and purification of phloroglucin and resorcinol 100 parts by weight of the acid cribage reaction product obtained in (3) above was neutralized with an aqueous NaOH solution, and then the solvent (acetone, water, toluene) was distilled off under high vacuum. did. Obtained pot residue (12
To 7 parts by weight of toluene and 5 parts by weight of water,
Was heated to the temperature of and stirred to obtain a solution. Next, the obtained solution was allowed to stand and separated into an oil layer and an aqueous layer, and then the oil layer solution and the aqueous layer solution were separated.

When the obtained aqueous layer solution was cooled to a temperature of 15 ° C,
1.1 parts by weight of brown crystals were precipitated. The crystals contained 69% by weight of phloroglucin, 15% by weight of resorcin, and 13% by weight of water.

Then, the crystals were dissolved again in boiling water, treated with activated carbon, recrystallized, and dried to obtain crystals of phloroglucin (white crystals, purity 99.0% by weight, melting point 219 ° C).

On the other hand, the oil layer solution obtained by stationary separation and the residual liquid after the crystallization of phloroglucin were added, the solvent was removed again, and the mixture was introduced into a distillation column with a sieve tray of 5 stages. After that, the bottom of the tower is 250 ℃
As a result of distilling resorcin under a reduced pressure of 5 to 20 Torr, a fraction containing 75% by weight of resorcin and 25% by weight of others was obtained. Toluene was added to 10 parts by weight of this fraction.
After adding 27 parts by weight and heating to a temperature of 95 ° C to dissolve, 40
When the resorcinol was crystallized by cooling to a temperature of ℃,
Resorcin crystals with a purity of 98% by weight (white crystals, melting point 110
° C).

Example 2 (1) Primary Oxidation Treatment In the same reaction vessel as in Example 1, TIPB333g, m-DIPB66 was added.
6 g of water, 400 g of water and 70 g of an aqueous NaOH solution (concentration 3.6% by weight) were charged, and the air oxidation reaction was carried out at a temperature of 100 ° C. for 35 hours in the same manner as in Example 1. The obtained oxidation reaction product (oil layer solution) was 2010 g (water content 36% by weight), and as oxides of TIPB, TRHP 9% by weight, HDHP 11% by weight and DHHP 3% by weight were contained, and m-DIPB The oxides were 30% by weight of m-DHP and 13% by weight of m-HHP.

The yield of the phloroglucin-based oxidation product based on TIPB calculated in the same manner as in Example 1 was 66 mol%, and m
-The yield of resorcin-based oxidation product based on DIPB was 63.
Mole%.

(2) H ₂ O ₂ oxidation step To 100 parts by weight of the oxidation product (mixture of oil layer and aqueous layer) obtained in (1) primary oxidation treatment, 64 parts by weight of toluene was added and heated to a temperature of 50 ° C. It was stirred.

The resulting solution was allowed to stand and separated, 128 parts by weight of the oil layer solution obtained by removing the aqueous layer solution was charged into a reactor equipped with a stirrer and a reflux condenser, and 24% by weight of H ₂ O ₂ was added thereto. And 12% by weight
Add 210 parts by weight of an aqueous solution containing sulfuric acid of
The reaction was carried out at a temperature of 0 ° C for 15 minutes. After completion of the reaction, 129 parts by weight of an oil layer solution and 209 parts by weight of an aqueous layer solution were obtained by separating oil and water. TRHP concentration in the oil layer solution is 9.4 wt%,
The m-DHP concentration was 20.1% by weight.

The phloroglucin-based H ₂ O ₂ oxidation yield calculated in the same manner as in Example 1 was 79 mol%, and the resorcin-based H ₂ O _{2 was obtained.}
The oxidation yield was 92 mol%.

The H ₂ O ₂ oxide was neutralized, washed with water, and further distilled off part of water and toluene to be concentrated, and then used in the next acid-carbage reaction. At this time, the concentration of toluene in the oil layer solution was 40% by weight.

On the other hand, the aqueous layer solution contained 22% by weight of H ₂ O ₂ and 12% by weight of sulfuric acid, which was dehydrated and concentrated under reduced pressure to give 60% by weight.
H ₂ O ₂ and concentrated sulfuric acid were added to adjust the concentration, and then H ₂ O ₂ was added again.
It was made available for the oxidation reaction.

(3) Cribage reaction step Acetone containing 0.06% by weight of phosphotungstic acid was added to a reactor equipped with a stirrer, a reflux condenser and a raw material supply port.
10 parts by weight of a solution (180 parts by weight) prepared by mixing 90 parts by weight of the oxidation reaction product obtained in the above (2) H ₂ O ₂ oxidation step and 90 parts by weight of acetone was added thereto while stirring. Added at a rate of parts / minute. During this period, the reaction temperature was maintained at a temperature at which acetone in the system was refluxed (initial 56 ° C, 65 ° C at the end of addition).
After the addition was completed, stirring was further continued at a temperature of 65 ° C. for 25 minutes to complete the reaction.

The concentration of phloroglucin in the reaction solution at the end of the reaction was
It was 0.92% by weight and the concentration of resorcin was 2.5% by weight.

The yield of phloroglucin relative to TRHP (TRHP standard) calculated in the same manner as in Example 1 was 63 mol%, and m-DH
The yield of resorcin on P was 90 mol%.

(4) Separation and Purification of Phloroglucin and Resorcinol 100 parts by weight of the acid clavage reaction product obtained in the above (3) Curvage reaction step was neutralized in the same manner as in Example 1, and then the solvent was distilled off under high vacuum. 7 parts by weight of toluene and 5 parts by weight of water were added to the obtained residue (12 parts by weight), and the mixture was heated to a temperature of 75 ° C. to be dissolved. After stirring, the solution was separated into an oil layer solution and an aqueous layer solution, and both were stirred and dissolved. Then, the solution was left still, and the separated oil layer solution and aqueous layer solution were separated.

When the obtained aqueous layer solution was cooled to a temperature of 15 ° C,
0.1 part by weight of brown crystals were precipitated. The crystals contained 65% by weight of phloroglucin, 17% by weight of resorcin, and 13% by weight of water. The crystals were dissolved again in boiling water, treated with activated carbon, recrystallized, and then dried to give crystals of phloroglucin (white crystals, purity 99.0% by weight,
Melting point 219 ° C.) was obtained.

On the other hand, the separated oil layer solution and the residual liquid after the crystallization of phloroglucin were added, the solvent was removed again, and the mixture was introduced into a distillation column with a sieve tray of 5 stages. Next, the bottom of the column was heated to a temperature of 250 ° C., and as a result of distilling resorcin under a reduced pressure of 5 to 20 Torr,
A fraction containing 77% by weight of resorcin and 23% by weight of others was obtained. To 10 parts by weight of this fraction, 27 parts by weight of toluene was added, and the mixture was heated to a temperature of 95 ° C to dissolve it, and then cooled to a temperature of 40 ° C to crystallize resorcinol, and the purity was 99% by weight.
Of resorcinol (white crystal, melting point 110 ° C.) was obtained.

[Brief description of the drawings]

FIG. 1 is a process diagram schematically showing one embodiment of a method for producing phloroglucin and resorcin according to the present invention. 1 ... Primary oxidation treatment step, 2 ... Secondary oxidation treatment step 3 ... Concentration step, 4 ... Cribage reaction step 5 ... Separation step

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location B01J 27/188 B01J 27/188 X C07B 61/00 300 C07B 61/00 300 C07C 29/50 9155- 4H C07C 29/50 33/26 9155-4H 33/26 409/08 9357-4H 409/08

Claims (1)

(57) [Claims] 1. A H ₂ O _{2 in} which a mixed solution containing an oxide of 1,3,5-triisopropylbenzene and an oxide of m-diisopropylbenzene is brought into contact with a hydrogen peroxide solution containing a first acidic catalyst. An oxidation step: and an acid decomposition step of bringing the reaction solution obtained from the above step into contact with a second acidic catalyst: A method for simultaneously producing phloroglucin and resorcin.